Cycling stability of the photochromic effect in rare-earth oxyhydride thin films is of great importance for long-term applications such as smart windows. However, an increasingly slower bleaching rate upon photochromic cycling was found in yttrium oxyhydride thin films; the origin of this memory effect is yet unclear. In this work, the microstructural changes under six photodarkening-bleaching cycles in YHxOy and GdHxOy thin films are investigated by in situ illumination Doppler broadening positron annihilation spectroscopy, complemented by positron annihilation lifetime spectroscopy (PALS) investigations on YHxOy films before and after one cycle. For the first three cycles, the Doppler broadening S parameter after bleaching increases systematically with photodarkening-bleaching cycle, and correlates with the bleaching time constant extracted from optical transmittance measurements. This suggests that the microstructural evolution that leads to progressively slower bleaching involves vacancy creation and agglomeration. PALS suggests that during a photodarkening-bleaching cycle, divacancies are formed that are possibly composed of illumination-induced hydrogen vacancies and preexisting yttrium monovacancies, and vacancy clusters grow, which might be due to local removal of hydrogen. If bleaching is a diffusion-related process, the formed vacancy defects induced by illumination might affect the diffusion time by reducing the diffusion coefficient. Hydrogen loss could also be a key factor in the reduced bleaching kinetics. Other microstructural origins including domain growth, or formation of OH- hydroxide groups, are also discussed with respect to the slower bleaching kinetics. During the fourth to sixth photodarkening-bleaching cycle, reversible shifts in the Doppler S and W parameters are seen that are consistent with the reversible formation of metallic-like domains, previously proposed as a key factor in the mechanism for the photochromic effect.

At ambient conditions, rare-earth oxyhydride thin films show reversible photochromism and photoconductivity, while their mechanism and relation are still unclear. In this work, this question is explored with in situ time-resolved measurements of both optical and transport properties of Gd-based oxyhydride thin films. It is found that p-type large polaron conduction is the initial mechanism of charge transport; however, upon photo-darkening, a 10⁴-fold increase of conductivity occurs, and n-type carriers become dominant. Further, photochromism and photoconductivity are shown to originate from a single process, as indicated by the fact that the photoconductivity is exponentially proportional to the increase of optical absorption. This exponential relation, notably, cannot stem from any of the optically absorbing species thought responsible for photochromism and, therefore, suggests that their formation is accompanied by a concerted increase of negative charge carriers in the Gd oxyhydride films.

Rare earth oxyhydrides REO_xH_(3-2x), with RE = Y, Sc, or Gd and a cationic FCC lattice, are reversibly photochromic in nature. It is known that structural details and anion (O^2-:H^-) composition dictate the efficiency of the photochromic behavior. The mechanism behind the photochromism is, however, not yet understood. In this study, we use ¹H, ²H, ¹⁷O, and ⁸⁹Y solid-state NMR spectroscopy and density functional theory (DFT) calculations to study the various yttrium, hydrogen, and oxygen local environments, anion oxidation states, and hydride ion dynamics. DFT models of YO_xH_(3-2x) with both anion-ordered and anion-disordered sublattices are constructed for a range of compositions and show a good correlation with the experimental NMR parameters. Two-dimensional ¹⁷O-¹H and ⁸⁹Y-¹H NMR correlation experiments reveal heterogeneities in the samples, which appear to consist of hydride-rich (x ≈ 0.25) and hydride-poor domains (x ≈ 1) rather than a single composition with homogeneous anion mixing. The compositional variation (as indicated by the different x values in YO_xH_(3-2x)) is determined by comparing static ¹H NMR line widths with calculated ¹H-¹H dipolar couplings of yttrium oxyhydride models. The 1D ¹⁷O MAS spectrum demonstrates the presence of a small percentage of hydroxide (OH^-) ions. DFT modeling indicates a reaction between the protons of hydroxides and hydrides to form molecular hydrogen (H⁺ + H^- → H₂). ¹H MAS NMR indicates the presence of a mobile component that, based on this finding, is attributed to trapped molecular H₂ in the lattice.

Rare-earth (RE) oxyhydride thin films show a color-neutral, reversible photochromic effect at ambient conditions. The origin of the photochromism is the topic of current investigations. Here, we investigated the lattice defects, electronic structure, and crystal structure of photochromic YHxOy and GdHxOy thin films deposited by magnetron sputtering using positron annihilation techniques and X-ray diffraction, in comparison with Y, YH∼1.9, Y2O3, Gd, GdH∼1.8, and Gd2O3 films. Positron annihilation lifetime spectroscopy (PALS) reveals the presence of cation monovacancies in the as-deposited Y and YH∼1.9 films at concentrations of ∼10-5 per cation. In addition, vacancy clusters and nanopores are found in the as-prepared YHxOy and Y2O3 films. Doppler broadening positron annihilation spectroscopy (DB-PAS) of the Y- A nd Gd-based films reflects the transition from a metallic to an insulating nature of the RE metal, metal hydride, semiconducting oxyhydride and insulating oxide films. In-situ illumination DB-PAS shows the irreversible formation predominantly of di-vacancies, as PALS showed that cation mono-vacancies are already abundantly present in the as-prepared films. The formation of di-vacancies supports conjectures that H-(and/or O2-) ions become mobile upon illumination, as these will leave anion vacancies behind, some of which may subsequently cluster with cation vacancies present. In addition, in RE oxyhydride films, partially reversible shifts in the Doppler parameters are observed that correlate with the photochromic effect and point to the formation of metallic domains in the semiconducting films. Two processes are discussed that may explain the formation of these metallic domains and the changes in optical properties associated with the photochromic effect. The first process considers the reversible formation of metallic nanodomains with reduced O: H composition by transport of light-induced mobile hydrogen and local oxygen displacements. The second process considers metallic nanodomains resulting from the trapping of photoexcited electrons in an eg orbital at the yttrium ions surrounding positively charged hydrogen vacancies that are formed by light-induced removal of hydrogen atoms from octahedral sites. When a sufficiently large concentration, on the order of ∼10%, is reached in a certain domain of the film, band formation of the eg electrons may occur, leading to an Anderson-Mott insulator-metal transition like the case of yttrium trihydride in these domains.

In this paper, we investigate by ab initio DFT how the O:H ratio influences the formation and lattice energy, metastability, and optical properties of Y and La anion-disordered ROxH3-2x oxyhydrides. To achieve this, a set of special quasirandom structures (SQS) is introduced to model anion-disorder along the whole RH3-R2O3 composition line. A comparison with an extensive set of anion-ordered polymorphs of the same composition shows the comparable energy of the anion-disordered phase, which, in particular, in the H-rich composition interval showed the lowest relative energy. In turn, the metastability of the anion-disordered phase depends on the cation size (Y versus La), which determines the maximum H content above which the CaF2-type structure itself becomes unstable. To overcome the accuracy limitations of classical DFT, the modified Becke-Johnson (mBJ) scheme is employed in the study of the electronic properties. We show that major differences occur between H-rich and O-rich R oxyhydrides, as the octahedral H- present for x<1 form electronic states at the top of the valence band, which reduce the energy band gap and dominate the electronic transitions at lower energies, thus increasing the refractive index of the material in the VIS-nIR spectral range. Comparing the DFT results to experimental data on photochromic Y oxyhydride films reinforces the hypothesis of anion-disorder in the H-rich films (x<1), while it hints towards some degree of anion ordering in the O-rich ones (x>1). Our paper exemplifies a strategy to calculate ab initio the electronic/optical properties of a wide range of materials with occupational disorder.

To develop an understanding of the photochromic effect in rare-earth metal oxyhydride thin films (REH3-2xOx, here RE = Y), we explore the aliovalent doping of the RE cation. We prepared Ca-doped yttrium oxyhydride thin films ((CazY1-z)HxOy) by reactive magnetron cosputtering with Ca doping concentrations between 0 and 36 at. %. All of the films are semiconductors with a constant optical band gap for Ca content below 15%, while the band gap expands for compositions above 15%. Ca doping affects the photochromic properties, resulting in (1) a lower photochromic contrast, likely due to a lower H- concentration, and (2) a faster bleaching speed, caused by a higher pre-exponential factor. Overall, these results point to the importance of the H- concentration for the formation of a "darkened"phase and the local rearrangement of these H- for the kinetics of the process.

The energy axes of the RBS and ERD data (contained in Figures 2a,b,d,e, and S4) were originally underestimated, and the corrected figures appear below and in the Supporting Information. The change is in the conversion from raw data to the energy scale, which was initially converted incorrectly. The rescaled x-axis does not change the data conclusions since the assignment of peaks to atoms remains the same and the intensity of the peaks is unaffected. Hence, it has no influence on the calculations and conclusions in the original text. (Figure presented).

Rare-earth oxyhydride REOxH3-2x thin films prepared by air-oxidation of reactively sputtered REH2 dihydrides show a color-neutral, reversible photochromic effect at ambient conditions. The present work shows that the O/H anion ratio, as well as the choice of the cation, allow to largely tune the extent of the optical change and its speed. The bleaching time, in particular, can be reduced by an order of magnitude by increasing the O/H ratio, indirectly defined by the deposition pressure of the parent REH2. The influence of the cation (RE = Sc, Y, Gd) under comparable deposition conditions is discussed. Our data suggest that REs of a larger ionic radius form oxyhydrides with a larger optical contrast and faster bleaching speed, hinting to a dependency of the photochromic mechanism on the anion site-hopping.

Thin films of rare earth metal oxyhydrides show a photochromic effect, the precise mechanism of which is yet unknown. Here, we made thin films of NdH3-2xOx and show that we can change the band gap, crystal structure, and photochromic contrast by tuning the composition (O2-:H-) via the sputtering deposition pressure. To protect these films from rapid oxidation, we add a thin ALD coating of Al2O3, which increases the lifetime of the films from 1 day to several months. Encapsulation of the films also influences photochromic bleaching, changing the time dependency from first-order kinetics. As well, the partial annealing which occurs during the ALD process results in a dramatically slower bleaching speed, revealing the importance of defects for the reversibility (bleaching speed) of photochromism.

Thin films of rare-earth metal oxyhydrides, such as yttrium oxyhydrides (YH3-2xOx), show a photochromic effect where the transparency of the films decreases reversibly upon exposure to UV light. However, the exact mechanism behind this effect is unknown. In this paper, we describe the behavior of YH3-2xOx thin films, with different O2-:H- ratios, under dark and illuminated conditions using in situ muon spin relaxation (μ+SR), and compare that to an oxygen-free reference compound, yttrium dihydride (YH2-δ). The muon acts as a local magnetic probe in our compounds, giving information related to electronic, structural, and photochromic properties. Although YH2-δ is the parent compound to YH3-2xOx, the muon behavior in these two materials is different - the muon electrostatically interacts primarily with H- (dihydride) or O2- (oxyhydride) - leading to the use of different theoretical models. For YH2-δ, we observed the formation of an entangled H-μ complex and the onset of Mu+ diffusion and H- rearrangement above 150 K (EA,Γ=67±13meV). For the oxyhydrides, we adopted a transition state model, where Mu0 formation and gradual Mu+ recovery take place, accompanied by the formation of a Mu+-O2- complex and a polaron at the Y cation. The activation energy (EA,dia) associated with Mu+ recovery is dependent on lattice relaxation and is lower for thin films of higher H content (EA,dia=29-45meV). In situ illumination further reduces this energy barrier for all measured oxyhydrides, suggesting that the photochromic effect involves a reversible structural rearrangement during photodarkening.

Doppler broadening positron annihilation spectroscopy depth profiles were collected on photochromic YO_xH_y thin films. In situ UV illumination of photochromic semiconductor YO_xH_y films leads to an increase in S-parameter and a large reduction in W-parameter, possibly caused by a change in the charge state of vacancies or the growth of hydrogen-rich metallic Y(O_x)H_y clusters, albeit that vacancy formation or changes in positronium formation during illumination might also play a role. Intriguingly, both the S- and W-parameters increase during thermal bleaching, indicating that another process takes place. The Doppler parameters do not return to their initial values after complete thermal bleaching, suggesting that persistent local rearrangements of vacancies and possibly hydride ions have occurred during the full photodarkening-thermal bleaching cycle. Positron annihilation lifetime spectroscopy shows that a small fraction of positronium is formed in as-deposited YO_xH_y films, indicating that the films contain some nanopores.

Rare-earth (RE) oxyhydride thin films prepared by reactive magnetron sputtering followed by air-oxidation show a color-neutral photochromic effect at ambient conditions within a wide composition range (REOxH3-2x where 0.5 ≤ x < 1.5). Due to the high degree of anion sublattice disorder present in these thin films, the structure models proposed for the related bulk materials are not directly applicable. Instead we use a combination of EXAFS analysis and lattice energy calculations to establish a fcc-based model linking the oxyhydrides to the related binary compounds. The oxide anions are found to occupy predominantly the tetrahedral sites in the fcc structure, which is attributed to electrostatic lattice energy minimization.

Thin films of rare-earth (RE)-oxygen-hydrogen compounds prepared by reactive magnetron sputtering show a unique color-neutral photochromic effect at ambient conditions. While their optical properties have been studied extensively, the understanding of the relationship between photochromism, chemical composition, and structure is limited. Here we establish a ternary RE-O-H composition-phase diagram based on chemical composition analysis by a combination of Rutherford backscattering and elastic recoil detection. The photochromic films are identified as oxyhydrides with a wide composition range described by the formula REO _x H _3-2x where 0.5 ≤ x ≤ 1.5. We propose an anion-disordered structure model based on the face-centered cubic unit cell where the O ^2- and H ^- anions occupy tetrahedral and octahedral interstices. The optical band gap varies continuously with the anion ratio, demonstrating the potential of band gap tuning for reversible optical switching applications.